Polyamide, electrophotographic photosensitive member employing the polyamide, and electrophotographic apparatus, device unit and facsimile machine employing the member

ABSTRACT

An electrophotographic photosensitive member, has an electroconductive support, an interlayer, and a photosensitive layer provided in the order named. The interlayer contains a polyamide having a structural unit represented by the formula (I) below: ##STR1## wherein R 1  is a substituted or unsubstituted alkyl group, R 2  is a substituted or unsubstituted alkylene group, and n is an integer of one or more.

This application is a division of application Ser. No. 07/874,833 filedApr. 28, 1992 now U.S. Pat. No. 5,419,993.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a polyamide of a novel structure and anelectrophotographic photosensitive member which has an interlayercontaining the polyamide.

The present invention also relates to an electrophotographic apparatus,a device unit, and a facsimile machine employing the electrophotographicphotosensitive member.

2. Related Background Art

In repeated use of a Carlson type electrophotographic photosensitivemember, one of the important characteristics of the member for stablyobtaining high-quality images is the stability of the dark areapotential and the light area potential. Therefore, improvement ofcarrier injection efficiency, improvement of adhesiveness of thephotosensitive layer to the support, improvement of coating propertiesof the photosensitive layer, and provision of an interlayer between asupport and a photosensitive layer to cover defects on the support havebeen proposed.

Known materials useful for the interlayer include polyamides(JP-A-Sho-46-47344 (The term "JP-A" as used herein means a JapanesePatent Laid-Open Application), JP-A-Sho-52-25638, andJP-A-Sho-58-95351), polyesters (JP-A-Sho-52-20836 and JP-A-54-26738),polyurethans (JP-A-Sho-49-10044 and JP-A-Sho-53-89435), casein(JP-A-Sho-55-103556), polypeptides (JP-A-Sho-53-48523), polyvinylalcohol (JP-A-Sho-52-100240), polyvinylpyrrolidone (JP-A Sho-48-30936),vinyl acetate-ethylene copolymers (JP-A-Sho-48-26141), maleic anhydrideester copolymers (JP-A-Sho-52-10138), polyvinylbutyral(JP-A-Sho-57-90639 and JP-A-Sho-58-106549), quaternaryammonium-containing polymers (JP-A-Sho-51-126149 and JP-A-Sho-56-60448)and ethylcellulose (JP-A-Sho-55-143564), and so forth.

The interlayer comprising the above-mentioned material, however, has theresistance susceptible to temperature and humidity, so that thestability of potential characteristics and high quality of images cannotalways be achieved over environmental conditions of from low temperatureand low-humidity to high temperature and high humidity.

For example, at low temperature and low humidity, the resistance of theinterlayer tends to become high, which may cause rise of a light-areapotential or a residual potential on repeated use of the photosensitivemember, thereby causing instability of image quality such as occurrenceof fogging (in positive development), and fall of image density (inreversal development).

On the other hand, at high temperature and high humidity, the resistanceof the interlayer tends to become low, which may cause lowering of thebarrier function to increase the carrier injection from the support sideand to lower the dark area potential, thereby causing black spot-likedefects or fogging of the image.

SUMMARY OF THE INVENTION

An object of the present invention is to provide a polyamide which has anovel structure and has a stable resistivity independently ofenvironmental conditions.

Another object of the present invention is to provide anelectrophotographic photosensitive member which has stable potentialcharacteristics and capable of giving stable images over a variety ofenvironmental conditions of from low temperature and low humidity tohigh temperature and high humidity.

A further object of the present invention is to provide anelectrophotographic apparatus, a device unit, and a facsimile machineemploying the electrophotographic photosensitive member.

The present invention provides polyamide having a structural unitrepresented by the formula (I) below: ##STR2## wherein R₁ is asubstituted or unsubstituted alkyl group, R₂ is a substituted orunsubstituted alkylene group, and n is an integer of one or more.

The present invention also provides an electrophotographicphoto-sensitive member, comprising an electroconductive support, aninterlayer, and a photosensitive layer provided in this order, theinterlayer containing a polyamide having a structural unit representedby the formula (I) below: ##STR3## wherein R₁ is a substituted orunsubstituted alkyl group, R₂ is a substituted or unsubstituted alkylenegroup, and n is an integer of one or more.

The present invention further provides an electrophotographic apparatus,a device unit, and a facsimile machine employing the above-specifiedelectrophotographic photosensitive member.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates roughly the constitution of an electrophotographicapparatus employing the photosensitive member of the present invention.

FIG. 2 illustrates an example of a block diagram of a facsimile systememploying the photosensitive member of the present invention.

DESCRIPTION OF THE PREFERRED EMBODIMENT

The polyamide of the present invention has a structural unit representedby the formula (I): ##STR4## wherein R₁ is a substituted orunsubstituted alkyl group, R₂ is a substituted or unsubstituted alkylenegroup, and n is an integer of one or more.

In the formula (I), the alkyl group represented by R₁ includes methyl,ethyl, propyl, etc., and the alkylene group represented by R₂ includesmethylene, ethylene, propylene, isopropylene, etc. The alkyl group andthe alkylene group may have a substituent such as a halogen atom, anaryl group such as phenyl, an alkoxy group, and the like.

The polyamide of the present invention is derived by substituting thehydrogen of the amide group of a polyamide resin as the main chain by asubstitution reaction to form a modified polyamide having the structuralunit represented by the formula (I).

The polyamide constituting the main chain of the modified polyamide ofthe present invention includes nylon resins such as 6, 11, 12, 66, and610, copolymer nylon resins containing the units of the above resins,N-alkoxymethylated or N-alkylated nylon resins, aromaticcomponent-containing nylon resins, and so forth.

The modified polyamide of the present invention may be crosslinked to beresistant to a paint solvent for photosensitive layer. The crosslinkingis usually practiced by heat treatment after coating film formation byuse of an epoxy compound, a melamine compound, or the like. In the casewhere an N-alkoxymethylated nylon resin is used as the polyamidecomponent, the crosslinking may be caused by self-crosslinking byheating with an acid catalyst such as citric acid, adipic acid, tartaricacid, maleic acid, phosphoric acid and hypophosphorus acid withoutcrosslinking agent.

The component of the main chain in the polyamide of the presentinvention is exemplified by the polymers having a structural unit asshown below, and the copolymers having two or more kinds of thestructural units shown below: ##STR5## (p and q represent respectivelyan integer of one or more).

Specific examples of the main chain components are listed below:

Examples of Components of Polyamide Main Chain

    ______________________________________                                                              Weight-average                                          Component                                                                             Kind of       molecular                                               example resin         weight     Remark                                       ______________________________________                                        I       6-nylon        95,000                                                 II      6, 66, 610    150,000    Component ratio                                      copolymer nylon          (by weight)                                                                   6/66/610 = 1/1/1                             III     6, 12, 66, 610                                                                              120,000    Component ratio                                      copolymer nylon          (by weight)                                                                   6/12/66/610 =                                                                 2/1/2/2                                      IV      N-methoxymethylated                                                                         210,000    Methoxymethyl                                        6-nylon                  substitution                                                                  ratio: 10 mol %                              ______________________________________                                    

Specific examples of preferred polyamides of the present invention areshown below without limiting the invention thereto.

The electrophotographic photosensitive member of the present inventioncontains the aforementioned modified polyamide resin in the interlayer,thereby being capable of preventing variation of the properties causedby variation of environmental conditions, such as rise of a residualpotential at low temperature and low humidity, and lowering of a barrierfunction and the resulting fall of a dark area potential.

The modified polyamide of the present invention has a volume resistancewhich is affected little by variation of environmental conditions.Therefore, the use of this resin in the interlayer enables preparationof an electrophotographic photosensitive member which hascharacteristics affected extremely little by variation of environmentalconditions. The resistance of an ordinary polyamide may be lower bythree decimals at a high temperature and a high humidity than that atordinary temperature and ordinary humidity. On the contrary, theresistance of the modified polyamide of the present invention isaffected only little by temperature and humidity.

The reasons why the properties of the modified polyamide of the presentinvention are affected little by environmental variation are consideredas below, although they are not proved.

(1) The polymer having a side chain is more readily transformed into anamorphous state or a network structure of the polymer than the linearpolymer to obtain a high ability of retaining an electroconductivesubstance such as water, ion, and the like in the interior of thecoating film formed, and forms a satisfactory film which is unlikely tocause film defects such as a pinhole.

(2) The polar group at the side chain promotes adsorption of water,ionic substance, etc., and improves adhesiveness of the film.

It is considered that from the above two factors the resistance does notrise even at a low temperature and a low humidity, and the amorphousstructure having a network prevents excessive incorporation of water orthe like to improve the film-forming properties and to cause noremarkable decrease of the resistance even at high temperature and highhumidity.

The modified polyamide of the present invention can be synthesized byreacting a polyamide as a starting material with a polyaldehyde and analcohol to introduce a substituent in place of a hydrogen of the amidogroup.

A specific Synthesis Example of a modified polyamide of the presentinvention is described below.

Synthesis Example 1 (Exemplified compound [1])

In a mixed solvent composed of 250 g of formic acid and 250 g of aceticanhydride, 50 g of 6-nylon resin was dissolved by agitation. Thereto, 15g of paraformaldehyde and 35 g of 2-methoxyethanol were added, and themixture was heated and reacted at 60° C. for 5 hours. The reactedsolution was cooled to room temperature and was poured into 5 liters ofacetone to precipitate the reaction product. The precipitated whiteproduct was collected by filtration. The resulting product was agitatedand washed in a large amount of water. The product was then collected byfiltration and vacuum-dried at 40° C. under a reduced pressure of from10 to 20 mmHg to obtain 50.7 g of methoxyethoxymethylated 6-nylon resin(methoxyethoxymethyl substitution ratio: 31%).

The interlayer of the present invention may be constituted solely of themodified polyamide, or may further contain another resin, an additive,an electroconductive substance, or the like. The resin which may becontained additionally in the interlayer includes polyamides such ascopolymer nylon and N-alkoxymethylated nylon, polyesters, polyurethanes,polyureas, and phenol resins. The additive includes powdery materialssuch as titanium oxide, alumina, and resins, surface active agents,leveling agents, and coupling agents.

The electroconductive substance includes powder, foil, and staple fiberof metals such as aluminum, copper, nickel and silver; electroconductivemetal oxides and solid solutions thereof such as antimony oxide, indiumoxide, and tin oxide; electroconductive polymer materials such aspolypyrrole, polyaniline and polyelectrolytes; carbon fiber; carbonblack; graphite powder; and electroconductive powdery material coatedwith the aforementioned electroconductive substance. From among these,electroconductive metal oxides are preferred.

The thickness of the interlayer of the present invention is selected, inconsideration of the electrophotographic characteristics and defects onthe support, within the range of from about 0.1 μm to 50 μm, usually andpreferably from 0.5 to 5 μm, and when an electroconductive substance isadded, preferably from 1 to 30 μm. The interlayer may be formed by acoating method such as immersion coating, spray coating, roll coating,and other coating methods.

A second interlayer mainly constituted of a resin may be provided on theinterlayer of the present invention, if necessary for control of abarrier function or for other purpose. The resin material for the secondinterlayer includes polyamides, polyesters, polyurethanes polyurea, andphenol resins as well as the modified polyamides of the presentinvention. The second interlayer has preferably a thickness of from 0.1to 5 μm, and may be formed by coating in a manner similar to theaforementioned interlayer.

The photosensitive layer in the present invention may be a monolayertype photosensitive layer which contains both a charge-generatingsubstance and a charge-transporting substance in one and the same layer,or otherwise may be a lamination type photosensitive layer which isconstituted of functionally separated layers comprising acharge-generating layer containing a charge-generating substance and acharge-transporting layer containing a charge-transporting substance.

The charge-generating layer can be formed by application and drying of adispersion of a charge-generating substance in a binder resin. Thecharge-generating substance includes azo pigments such as Sudan Red andDian Blue; quinone pigments such as pyrene quinone and anthanthorone;quinocyanine pigments; perylene pigments; indigo pigments such as indigoand thioindigo; azulenium salts; phthalocyanine pigments such as copperphthalocyanine and oxytitanium phthalocyanine, and the like. The binderresin includes polyvinylbutyral, polystyrene, polyvinyl acetate, acrylicresins, polyvinylpyrrolidone, ethylcellulose, cellulose acetatebutyrate, and the like. The charge-generating layer may be formed alsoby vapor deposition of the above-mentioned charge-generating substance.The thickness of the charge-generating layer is preferably not more than5 μm, more preferably in the range of from 0.05 to 2 μm.

The charge-transporting layer can be formed by application and drying ofa coating liquid prepared by dissolving a charge-transporting substancein a film-forming resin. The charge-transporting substance includespolycyclic aromatic compounds having a structure of biphenylene,anthracene, pyrene, phenanthrene, or the like in the main chain or theside chain thereof; nitrogen-containing cyclic compounds such as indole,carbazole, oxadiazole and pyrazoline; hydrazone compounds; styrylcompounds; and the like. The charge-transporting layer is prepared inthe manner above, because the charge-transporting substance is generallyof a low molecular weight and has poor film-forming properties byitself. The film-forming resin includes polyesters, polycarbonates,polymethacrylate esters, polystyrenes, etc. The thickness of thecharge-transporting layer is preferably in the range of from 5 to 40 μm,more preferably from 10 to 30 μm.

Furthermore, the photosensitive layer in the present invention includesorganic photoconductive polymer layers composed of polyvinylcarbazole,polyvinylanthracene, etc., selenium vapor deposition layers,selenium-tellurium vapor deposition layers, amorphous silicon layers,and the like.

The charge-generating layer may be provided on the charge-transportinglayer, or otherwise the charge-transporting layer may be provided on thecharge-generating layer.

The monolayer type photosensitive layer can be formed by application anddrying of a coating liquid prepared by dispersing and dissolving theaforementioned charge-generating substance and the charge-transportingsubstance in the aforementioned binder resin. The thickness of thephotosensitive layer is preferably in the range of from 5 to 40 μm, morepreferably from 10 to 30 μm.

The method of application of the photosensitive layer is similar to themethod for the interlayer.

Further on the photosensitive layer, a simple resin layer or a resinlayer containing the aforementioned electroconductive substance may beprovided as a protecting layer in the present invention.

The electroconductive support in the present invention may be made ofany material that is electroconductive, including metals and alloys suchas aluminum, copper, chromium, nickel, zinc, stainless steel, etc.;laminates of metal foil such as of aluminum and copper with a plasticfilm; plastic films having aluminum, indium oxide, tin oxide, or thelike vapor-deposited thereon; metals, plastics, and paper sheets havingan electroconductive layer formed by application and drying of anelectroconductive substance solely or with a binder resin; and so forth.

The electroconductive substance for the electroconductive layer includespowder, foil, and staple fiber of metals such as aluminum, copper,nickel and silver; electroconductive metal oxides and solid solutionsthereof such as antimony oxide, indium oxide, and tin oxide;electroconductive polymer materials such as polypyrrole, polyaniline,and polymer electrolytes; carbon fiber; carbon black; graphite powder;organic and inorganic electrolytes; and electroconductive powderymaterial prepared by coating with the aforementioned electroconductivesubstance; and so forth.

The binder resin for the electroconductive layer includes thermoplasticresins such as polyamides, polyesters, acrylic resins, polyvinyl acetateresins, polycarbonates, polyvinylformal resins, polyvinylbutyral resins,polyvinyl alkyl eters, polyalkylene ethers, and polyurethane elastomers,and thermosetting resins such as thermosetting polyurethanes, phenolresins, and epoxy resins.

The mixing ratio of the electroconductive substance to the binder resinis in the range of from 5:1 to 1:5. The mixing ratio is selected inconsideration of the resistivity, surface properties, coatingproperties, and other properties of the electroconductive layer.

If the electroconductive substance is powdery, the mixture is repairedin a conventional manner by means of a ball mill, a roll mill, a sandmill, or the like.

Further, another additive such as a surfactant, a silane coupling agent,a titanate coupling agent, a silicone oil, and a silicone leveling agentmay be added.

The electrophotographic photosensitive member of the present inventionis not only useful for electrophotographic copying machines but alsouseful widely in electrophotographic fields including laser beamprinters, CRT printers, LED printers, liquid crystal printers,electrophotographic engraving systems, and so forth.

FIG. 1 illustrates roughly an example of the constitution of anelectrophotographic apparatus employing the photosensitive member of thepresent invention.

In FIG. 1, a drum type photosensitive member 1 serves as an imagecarrier, being driven to rotate around the axis 1a in the arrowdirection at a predetermined peripheral speed. The photosensitive member1 is charged positively or negatively at the peripheral face uniformlyduring the rotation by an electrostatic charging means 2, and thenexposed to image-exposure light L (e.g. slit exposure, laserbeam-scanning exposure, etc.) at the exposure portion 3 with animage-exposure means (not shown in the drawing), whereby electrostaticlatent images are sequentially formed on the peripheral surface of thephotosensitive member in accordance with the exposed image.

Thus formed electrostatic latent image is developed with a toner by adeveloping means 4. The toner-developed images are sequentiallytransferred by a transfer means 5 onto a surface of a transfer-receivingmaterial P which is fed between the photosensitive member 1 and thetransfer means 5 synchronously with the rotation of the photosensitivemember 1 from a transfer-receiving material feeder not shown in thedrawing.

The transfer-receiving material P having received the transferred imageis separated from the photosensitive member surface, and introduced toan image fixing means 8 for fixation of the image and sent out of thecopying machine as a duplicate copy.

The surface of the photosensitive member 1, after the image transfer, iscleaned with a cleaning means 6 to remove any remaining un-transferredtoner, and is treated for charge elimination with a pre-exposure means 7for repeated use for image formation.

The generally employed charging means 2 for uniformly charging thephotosensitive member 1 is a corona charging apparatus. The generallyemployed transfer means 5 is also a corona charging means. In theelectrophotographic apparatus, two or more of the constitutionalelements of the above described photosensitive member, the developingmeans, the cleaning means, etc. may be integrated into one device unit,which may be made demountable from the main body of the apparatus. Forexample, at least one of the charging means, the developing means, andthe cleaning means is combined with the photosensitive member 1 into onedevice unit which is demountable from the main body of the apparatus byaid of a guiding means such as a rail in the main body of the apparatus.An electrostatic charging means and/or a developing means may becombined with the aforementioned device unit.

In the case where the electrophotographic-apparatus is used as a copyingmachine or a printer, the light L for optical image exposure may beprojected onto the photosensitive member as reflected light ortransmitted light from an original copy, or otherwise the informationread out by a sensor from an original may be signalized, and accordingto the signalized information light is projected onto a photosensitivemember, by scanning with a laser beam, driving an LED array, or drivinga liquid crystal shutter array.

In the case where the electrophotographic apparatus is used as a printerof a facsimile machine the optical image exposure light L is forprinting the received data. FIG. 2 is a block diagram of an example ofthis case.

A controller 11 controls the image-reading part 10 and a printer 19. Theentire of the controller 11 is controlled by a CPU 17. Readout data fromthe image reading part 10 is transmitted through a transmitting circuit13 to the other communication station. Data received from the othercommunication station is transmitted through a receiving circuit 12 to aprinter 19. The image data is stored in image memory 16. A printercontroller 8 controls a printer 19. The numeral 14 denotes a telephoneset.

The image received through a circuit 15, namely image information from aremote terminal connected through the circuit, is demodulated by thereceiving circuit 12, treated for decoding of the image information inCPU 17, and successively stored in the image memory 16. When at leastone page of image information has been stored in the image memory 16,the images are recorded in such a manner that the CPU 17 reads out theone page of image information, and sends out the decoded one page ofinformation to the printer controller 18, which controls the printer 19on receiving the one page of information from CPU 17 to record the imageinformation.

During recording by the printer 19, the CPU 17 receives the subsequentpage of information.

Images are received and recorded in the manner as described above.

The present invention is described in more detail by reference toExamples. The term "part" as the unit in Examples is based on weight.

EXAMPLE 1 (Synthesis of a polyamide modified by HOCH₂ CH₂ OCH₃)

In a 2-liter autoclave, 100 g of 6-nylon, 376 g of methylcellosolve, and80 g of paraformaldehyde were placed and were stirred at 120° C.,thereby the starting 6-nylon being dissolved.

Thereto, a mixture of 25 g of methylcellosolve and 1 g of phosphoricacid was added, and the reaction was allowed to proceed at 120° C. for45 minutes. The reaction mixture was poured into water, and leftstanding overnight. The resulting resin in a viscous lump state wastaken out and crushed. The crushed resin was washed with an alkalinesolution and repeatedly with water, and was air-dried. Then the resinwas dissolved in 200 g of methanol. After the insoluble matter waseliminated by filtration, the resin solution was poured into water. Thesolidified resin was crushed, and was washed with water repeatedly untilthe formaldehyde became undetectable by Schiff's reagent, and was thendried. Thus 80 g of dried resin was obtained. The modification ratio was30%. The resin was subjected to IR spectrum measurement and NMR spectrummeasurement, and the characteristic data as below were obtained.

IR spectrum (cm⁻¹): 1050-1100 (--C--O--C--)

    ______________________________________                                        .sup.13 C-NMR spectrum (ppm):                                                                     78 (--N--CH.sub.2 O--)                                                        65, 68 (--O--CH.sub.2 --)                                                     58 (--O--CH.sub.3)                                        ______________________________________                                    

The surface resistivity of the resulting modified polyamide was measuredaccording to JIS K6911. The quantity of triboelectrfication wasindicated by the saturated charging quantity measured at a load of 300g.

The results are shown in Table 1.

EXAMPLE 2 (Synthesis of a polyamide modified by HOCH₂ CH₂ OC₄ H₉)

A modified polyamide was prepared in an amount of 75 g at a modificationratio of 25% in the same manner as in Example 1 except that 100 g of6-nylon, 100 g of pareformaldehyde, 400 g of butylcellosolve (totalweight), and 2 g of phosphoric acid were used, and the reaction wasconducted at a temperature of 140° C. for one hour.

¹³ C-NMR spectrum (ppm): 60-70 (--O--CH₂ --)

The resulting modified polyamide was evaluated in the same manner as inExample 1. The results are shown in Table 1.

EXAMPLE 3 (Synthesis of a polyamide modified by HOCH₂ CH₂ OCH₂ CH₂ OC₂H₅)

A modified polyamide was prepared in an amount of 85 g at a modificationratio of 15% in the same manner as in Example 1 except that 100 g of6-nylon, 300 g of diethyleneglycol monoethyl ether, 100 g ofparaformaldehyde, and 4 g of phosphoric acid were used, and the reactionwas conducted at a temperature of 130° C. for one hour.

IR spectrum (cm⁻¹): 1050-1100 (--C--O--C--)

    ______________________________________                                        .sup.13 C-NMR spectrum (ppm):                                                                     65, 68 (--O--CH.sub.2 --)                                                     14 (--CH.sub.3)                                           ______________________________________                                    

The resulting modified polyamide was evaluated in the same manner as inExample 1. The results are shown in Table 1.

EXAMPLE 4 (Synthesis of a polyamide modified by HOCH₂ CH₂ OCH₂ --C6H₅)

A modified polyamide was prepared in an amount of 80 g at a modificationratio of 15% in the same manner as in Example 1 except that 100 g of6-nylon, 100 g of paraformaldehyde, 400 g of ethyleneglycol monobenzylether, and 4 g of phosphoric acid were used, and the reaction wasconducted at a temperature of 160° C. for 2 hours.

IR spectrum (cm⁻¹): 1580 (phenyl)

The resulting modified polyamide was evaluated in the same manner as inExample 1. The results are shown in Table 1.

EXAMPLE 5 (Synthesis of a polyamide modified by HOCH₂ CH₂ OCH₂ CH₂ OCH₃)

In a 1-liter autoclave, 100 g of 6-nylon, 250 g of diethyleneglycolmonomethyl ether, and 100 g of paraformaldehyde were placed, and themixture was stirred at 130° C. Thereto a mixture of 25 g ofdiethyleneglycol monomethyl ether and 4 g of phosphoric acid wascharged, and the reaction was allowed to proceed at 130° C. for 60minutes. The reaction mixture was poured into water, and the product wastreated in the same manner as in Example 1. Consequently, 95 g of amodified polyamide was obtained at a modification ratio of 15%.

IR spectrum (cm⁻¹): 1050-1100 (--C--O--C--)

    ______________________________________                                        .sup.13 C-NMR spectrum (ppm):                                                                     78 (--N--CH.sub.2 O--)                                                        65, 68 (--O--CH.sub.2 --)                                                     58 (--O--CH.sub.3)                                        ______________________________________                                    

The resulting modified polyamide was evaluated in the same manner as inExample 1. The results are shown in Table 1.

COMPARATIVE EXAMPLE 1

The modified polyamide obtained by using methoxymethylated nylon wasevaluated in the same manner as in Example 1. The results are shown inTable 1.

COMPARATIVE EXAMPLE 2

The modified polyamide obtained by using 6,66-nylon was evaluated in thesame manner as in Example 1. The results are shown in Table 1.

EXAMPLE 6

A paint for the electroconductive layer was prepared by dispersing 50parts of electroconductive titanium oxide powder coated with tin oxidecontaining 10% of antimony oxide, 25 parts of phenol resin, 20 parts ofmethylcellosolve, 5 parts of methanol, and 0.002 part of silicone oil(polydimethylsiloxane-polyoxyalkylene copolymer, average molecularweight 3,000) by means of a sand mill employing glass beads of 1 mmdiameter for 2 hours.

Onto an aluminum cylinder (30 mm diameter, 260 mm long), the above paintwas applied by immersion coating, and the coating was dried at 140° C.for 30 minutes to form an electroconductive layer of 20 μm thick.

A paint for an interlayer was prepared by dissolving 5 parts of theresin of aforementioned Resin Example [1] in 95 parts of methanol. Thispaint was applied on the above electroconductive layer by immersioncoating, and the resulting coating was dried at 90° C. for 10 minutes toform an interlayer of 0.6 μm thick.

A liquid dispersion for the charge-generating layer was prepared bydispersing 3 parts of the disazo pigment of the structural formulabelow: ##STR6## 2 parts of polyvinylbenzal (benzalation degree: 75%,weight-average molecular weight: 13,000), and 35 parts of cyclohexanoneby means of a sand mill employing glass beads of 1 mm diameter for 8hours, and then adding thereto 60 parts of methyl ethyl ketone (MEK).This liquid dispersion was applied on the above interlayer by immersioncoating, and was dried at 80° C. for 20 minutes to form acharge-generating layer of 0.2 μm thick.

A paint for the charge-transporting layer was prepared by dissolving 10parts of the styryl compound of the structural formula below: ##STR7##and 10 parts of polycarbonate (weight-average molecular weight: 46,000)in a mixed solvent of 10parts of dichloromethane and 40 parts ofmonochlorobenzene. This paint was applied on the above charge-generatinglayer by immersion coating, and dried at 120° C. for 60 minutes to forma charge-generation layer of 18 μm thick.

The electrophotographic photosensitive member thus prepared was mountedon a laser printer of reversal development type which conducts printingthrough a cyclic process ofcharging-exposure-development-transfer-cleaning at a cycle time of 2.0seconds, and the electrophotographic properties were evaluated atenvironmental conditions of normal temperature and normal humidity (23°C., 50% RH), and high temperature and high humidity (30° C., 85% RH).

As shown in Table 2, the photosensitive member of the present inventiongave a large difference between the dark area potential (V_(D)) and thelight area potential (V_(L)) resulting in a sufficient potentialcontrast, exhibiting a stable dark area potential (V_(D)) even at hightemperature and high humidity, and thus giving satisfactory quality ofimages without black dot defects nor fogging.

EXAMPLES 7-10

Electrophotographic photosensitive members of Examples 7 to 10 wereprepared in the same manner as in Example 6 except that the modifiedpolyamide of Resin Examples [2], [3], [5] and [6] were used respectivelyin place of the Resin Example [1] for the paint for the interlayers.

The resulting photosensitive members were evaluated in the same manneras in Example 6. Any of the photosensitive member had a stable dark-areapotential (V_(D)) even at high temperature and high humidity, and gaveexcellent images without a black dot defect nor fogging.

The results are shown in Table 2.

COMPARATIVE EXAMPLE 3

An electrophotographic photosensitive member was prepared in the samemanner as in Example 6 except that N-methoxymethylated 6-nylon(weight-average molecular weight: 120,000, methoxymethyl substitutionratio: 33%) was used in place of the modified polyamide of the presentinvention for the paint for the interlayer.

The resulting photosensitive member was evaluated in the same manner asin Example 6. At high temperature and high humidity, the dark areapotential (V_(D)) of the photosensitive member decreased, and black dotdefects were observed in the images.

The results are shown in Table 2.

EXAMPLE 11

A paint for the interlayer was prepared by dissolving 5 parts of theresin of Resin Example[9] in 95 parts of methanol.

This resin was applied onto an aluminum cylinder (30 mm diameter, 360 mmlong), and was dried at 100° C. for 20 minutes to form an interlayer of1.2 μm thick.

A liquid dispersion for the charge generating layer was prepared bydispersing 4 parts of oxytitanium phthalocyanine pigment, 3 parts ofpolyvinylbutyral (butyralation degree: 68%, weight-average molecularweight: 24,000), and 34 parts of cyclohexanone by means of a sand millemploying glass beads of 1 mm diameter for 10 hours, and the addingthereto 60 parts of tetrahydrofuran (THF). This dispersion was appliedon the above interlayer by immersion coating, and dried at 80° C. for 15minutes to form a charge-generating layer of 0.15 μm thick.

A paint for a charge-transporting layer was prepared by dissolving 7parts of the styryl compound used in Example 6 and 10 parts ofpolycarbonate (weight-average molecular weight: 59,000) in a mixedsolvent of 15 parts of dichloromethane and 45 parts ofmonochlorobenzene. This solution was applied on the abovecharge-generating layer by immersion coating, and was dried at 120° C.for 60 minutes to form a charge-transporting layer of 25 μm thick.

The electrophotographic photosensitive member thus prepared was mountedon a laser printer of a reversal development type which conductsprinting through a cyclic process ofcharging-exposure-development-transfer cleaning at a cycle time of 0.6second, and the electrophotographic properties were evaluated atenvironmental conditions of low temperature and low humidity (15° C.,10% RH).

As shown in Table 3, this photosensitive member gave a large differencebetween the dark area potential (V_(D)) and the light area potential(V_(L)), resulting in a sufficient potential contrast. During 1000sheets of continuous image formation, the rise of the light areapotential (V_(L)) was little, and images were formed stably.

EXAMPLES 12-15

Electrophotographic photosensitive members of Examples 12 to 15 wereprepared in the same manner as in Example 11 except that the modifiedpolyamide of Resin Examples [10], [16], [29] and [33] were usedrespectively in place of the Resin Example [9] for the paint for theinterlayers.

The resulting photosensitive members were evaluated in the same manneras in Example 11. Any of the photosensitive members gave a largedifference between the dark area potential (V_(D)) and the light areapotential (V_(L)); resulting in a sufficient potential contrast. During1000 sheets of continuous image formation, the rise of the light areapotential (V_(L)) was little, and images were formed stably.

The results are shown in Table 3.

COMPARATIVE EXAMPLE 4

An electrophotographic photosensitive member was prepared in the samemanner as in Example 6 except that alcohol-soluble copolymer nylon(weight-average molecular weight: 66,000) was used for the paint for aninterlayer in place of the modified polyamide of the present invention.

This photosensitive member was evaluated in the same manner as inExample 11. During 1000 sheets of continuous image formation, the lightarea potential (V_(L)) became higher and came to cause fogging.

The results are shown in Table 3.

EXAMPLE 16

A paint for an interlayer was prepared by dispersing 25 parts ofelectroconductive titanium oxide powder coated with tin oxide containing10% of antimony oxide, 20 parts of futile type titanium oxide powder, 20parts of the resin of the Resin Example [13], 20 parts of methanol, and10 parts of 2-propanol by means of a sand mill employing glass beads of1 mm diameter for 4 hours.

Onto an aluminum cylinder (60 mm diameter, 260 mm long), the above paintwas applied by immersion coating, and was dried at 160° C. for 30minutes to form an interlayer of 16 μm thick.

A paint for a second interlayer was prepared by dissolving 5 parts ofalcohol-soluble copolymer nylon (weight-average molecular weight:66,000) in 95 parts of methanol. This paint was applied on the aboveinterlayer-by-immersion coating, and was dried at 90° C. for 15 minutesto form a second interlayer of 0.3 μm thick.

A liquid dispersion for the charge-generating layer was prepared bydispersing 2 parts of the disazo pigment of the structural formulabelow: ##STR8## 1 part of polyvinylbutyral (butyralation degree: 68%,weight-average molecular weight: 18,000), and 30 parts of cyclohexanoneby means of a sand mill employing glass beads of 1 mm diameter for 20hours, and adding thereto 65 parts of methyl ethyl ketone (MEK). Thisliquid dispersion was applied on the above second interlayer byimmersion coating, and was dried at 80° C. for 20 minutes to form acharge-generating layer of 0.2 μm thick.

A paint for the charge-transporting layer was prepared by dissolving 9parts of the hydrazone compound of the structural formula below:##STR9## and 10 parts of polycarbonate (weight-average molecular weight:46,000) in a mixed solvent of 20 parts of dichloromethane and 40 partsof monochlorobenzene. This paint was applied on the abovecharge-generating layer by immersion coating, and dried at 120° C. for60 minutes to form a charge-transporting layer of 23 μm thick.

The electrophotographic photosensitive member thus prepared was mountedon a laser printer of reversal development type which conducts printingthrough a cyclic process ofcharging-exposure-development-transfer-cleaning at a cycle time of 0.8seconds, and the electrophotographic properties were evaluated atenvironmental conditions of low temperature and low humidity (15° C.,10% RH).

As shown in Table 4, this photosensitive member gave a large differencebetween the dark area potential (V_(D)) and the light area potential(V_(L)), resulting in a sufficient potential contrast. During continuous1000 sheets of image formation, the rise of the light area potential(V_(L)) was little, and satisfactory images were formed stably.

EXAMPLE 17

An electrophotographic photosensitive member was prepared throughformation of an interlayer, a charge-generating layer, and acharge-transporting layer in the same manner as in Example 16 exceptthat the second interlayer was not provided.

This photosensitive member was evaluated in the same manner as inExample 16. This photosensitive member gave a large difference betweenthe dark area potential (V_(D)) and the light area potential (V_(L)),resulting in a sufficient potential contrast. During continuous 1000sheets of image formation, the rise of the light area potential (V_(L))was little, and satisfactory images were formed stably.

The results are shown in Table 4.

COMPARATIVE EXAMPLES 5 and 6

Electrophotographic photosensitive members of Comparative Examples 5 and6 were prepared, in the same manner as in Examples 16 and 17 exceptthat, in the paint for the interlayer containing electroconductivetitanium oxide powder and rutile type titanium oxide powder, a phenolresin was used in place of the modified polyamide of Example 16.

These Photosensitive members were evaluated in the same manner as inExample 16. As shown in Table 4, in Comparative Example 5, the lightarea potential (V_(L)) rises and the formed images came to be foggedduring 1000 sheets of continuous copying. In Comparative Example 6 inwhich the charge-generating layer and the charge-transporting layer weredirectly provided on the interlayer, the barrier function of theinterlayer was insufficient, therefore the charge injection from thesupport side being increased and the dark area Potential (V_(D)) beinglowered. Consequently potential contrast necessary for image formationcould not be obtained.

    __________________________________________________________________________                                           Substitution                                <Main Chain>                      Ratio for                              Resin                                                                              Polyamide Resin                                                                        <Side Chain>             Modification                           Example                                                                            Component                                                                              Component of Modified Portion                                                                          (wt %)                                 __________________________________________________________________________     1  2  3  4                                                                        I II III IV                                                                             ##STR10##               31 27 36 18                             5  6  7  8                                                                        I II III IV                                                                             ##STR11##               30 34 33 15                             9 10 11 12                                                                        I II III IV                                                                             ##STR12##               36 39 41 17                            13 14 15 16                                                                        I II III IV                                                                             ##STR13##               33 40 35 16                            17 18 19 20                                                                        I II III IV                                                                             ##STR14##               43 45 35 19                            21 22 23 24                                                                        I II III IV                                                                             ##STR15##               35 31 31 20                            25 26                                                                              I II                                                                                    ##STR16##               31 24                                  27 28                                                                              III IV                                                                                  ##STR17##               25 17                                  29 30                                                                              II IV                                                                                   ##STR18##               15 12                                  31 32                                                                              III IV                                                                                  ##STR19##               23 15                                  33   III                                                                                     ##STR20##               35                                     34   III                                                                                     ##STR21##               33                                     __________________________________________________________________________

                  TABLE 1                                                         ______________________________________                                                 Surface           Tribo-                                                      Resistivity (Ω)                                                                           electrification (V)                                         23° C./                                                                       23° C./                                                                           23° C./                                                                        23° C./                                      55% rh 15% rh     55% rh  15% rh                                     ______________________________________                                        Example                                                                       1          4.2 × 10.sup.9                                                                   5.1 × 10.sup.9                                                                     0     0                                        2          2.6 × 10.sup.9                                                                   9.8 × 10.sup.9                                                                     0     0                                        3          3.7 × 10.sup.9                                                                   2.1 × 10.sup.9                                                                     0     0                                        4          1.5 × 10.sup.9                                                                   2.2 × 10.sup.10                                                                    0     0                                        5          3.5 × 10.sup.9                                                                   2.0 × 10.sup.10                                                                    0     0                                        Comparative                                                                   Example                                                                       1          4.5 × 10.sup.10                                                                  1.2 × 10.sup.12                                                                    0     130                                      2          3.3 × 10.sup.13                                                                  1.2 × 10.sup.14                                                                    150   340                                      ______________________________________                                    

                  TABLE 2                                                         ______________________________________                                        23° C., 50% RH                                                                              30° C., 85% RH                                    Dark Area     Light Area Dark Area                                            Potential V.sub.D                                                                           Potential V.sub.L                                                                        Potential V.sub.D                                                                        Image                                     (-V)          (-V)       (-V)       Quality                                   ______________________________________                                        Example 6                                                                             670       190        645      Good                                    Example 7                                                                             680       185        650      Good                                    Example 8                                                                             680       175        635      Good                                    Example 9                                                                             700       180        680      Good                                    Example 10                                                                            670       175        645      Good                                    Comparative                                                                           670       210        570      Black-                                  Example 3                             dotted                                  ______________________________________                                    

                  TABLE 3                                                         ______________________________________                                                             After Continuous                                         Initial Stage        1000-sheet Copying                                       Dark Area     Light Area Light Area                                           Potential V.sub.D                                                                           Potential V.sub.L                                                                        Potential V.sub.L                                                                        Image                                     (-V)          (-V)       (-V)       Quality                                   ______________________________________                                        Example 11                                                                            590       160        170      Good                                    Example 12                                                                            610       165        170      Good                                    Example 13                                                                            580       170        185      Good                                    Example 14                                                                            580       155        170      Good                                    Example 15                                                                            570       150        160      Good                                    Comparative                                                                           600       180        330      Fogging                                 Example 4                                                                     ______________________________________                                    

                  TABLE 4                                                         ______________________________________                                                                After Continuous                                                  Initial Stage                                                                             1000-sheet Copying                                                  Dark Area                                                                              Light Area                                                                             Light Area                                                  Potential                                                                              Potential                                                                              Potential                                            Second V.sub.D  V.sub.L  V.sub.L                                                                              Image                                         Interlayer                                                                           (-V)     (-V)     (-V)   Quality                                ______________________________________                                        Example 16                                                                             Provided 670      160    170    Good                                 Example 17                                                                             None     650      160    175    Good                                 Comparative                                                                            Provided 690      165    410    Fogging                              Example 5                                                                     Comparative                                                                            None     200       30    (Evaluation                                 Example 6                         impracticable)                              ______________________________________                                    

What is claimed is:
 1. A polyamide having a structural unit representedby formula (I) below: ##STR22## wherein R₁ is alkyl or alkyl substitutedwith halogen, aryl or alkoxy, R₂ is alkylene or alkylene substitutedwith halogen, aryl or alkoxy and n is an integer of one or more.